Binding agent for linoleum



Patented May 6, 1941 BINDING AGENT FOR LINOLEUBI Abraham B. Miller, Newark, Del., assignor to Hercules Powder Company, Wilmington, DeL, a

corporation of Delaware No Drawing. Application August 27, 1938, Serial No. 227,058

14 Claims.

This invention relates to an oleoresinous composition adapted for use as a binding agent for sequent uselessness in a relatively short time.

Apart from the action of alkalies, such floor coverings are inclined to be too soft to withstand heavy weights especially under sub-tropical and tropical conditions.

The present invention has for an object a binding agent which will produce a floor covering with an improved resistance to weak alkalies and moisture, making possible a floor covering having increased life in service.

In accordance with my invention, my binding agent comprises the reaction product of petroleum hydrocarbon-insoluble resin derived from pine wood, a drying oil or a semi-drying oil and a converting agent, specifically, an aldehyde with or without an alkaline catalyst. The drying or semi-drying oils modified in this manner yield an elastic gel product which is an improvement over the prior art oxidized plastics or binding agents 2 for linoleum, in that it has an improved resistance to moist, warm conditions and alkalies. Furthermore, it is possible to use high concentrations of fish oils in the preparation of my linoleum plastics without deleterious results. The prior art has attempted to use fish oils, such as, for example, Menhaden oil, in the preparation of binding agents but the use of any appreciable quantities of these oils has increased rather than decreased the deficiencies of the binding agents. In addition, prior art binding agents with appreciable quantities of fish oils have produced linoleum mixes having poor fabricating qualities. My binding agents may be mixed with ground cork, wood flour and other fillers to form a surfacing material on burlap in the fabrication of inlaid, granulated or plain linoleums, or to form a surfacing material on saturated felt to fabricate a linoleum-like floor covering.

In proceeding to make my binding agent, subsequently to' be used in linoleum compounding, I heat petroleum hydrocarbon-insoluble resin derived from pine wood with a drying or semidrying oil at a temperature from about 570 F. to about 590 F. for about A; hour to effect preliminary combination. I then lower the temperature to about 525 F. and hold at that temperature for approximately 4-5 hours. At the end of this time the material will be of a heavy, sticky pitch-like consistency, and the addition of a minor amount of an aldehyde with or Without an alkaline catalyst converts this pitch-like material to one having an elastic gel structure, which is the binding agent used for linoleum compounding.

With regard to the converting agent, it is desirable to take the precaution of not adding this before the oleoresinous composition has reached a stage of polymerization such that the said composition assumes an elastic gel structure after the converting agent is added thereto. I have found, for example, that if this is added at the end of 3 hours, no action except a slight thickening occurs. The point to add the agent is conveniently determined by withdrawing a small sample, adding the converting agent thereto, maintaining this at about 400 F. to about 525 F. and determining whether this small sample will gel. If it does, said agent in proper amount may be added to the larger batch.

The binder, as prepared above, may be used alone or it may be blended with the orthodox linoleum binder heretofore used. If blended with the latter, the preferable resin concentration of my plastic will be within the range of about 10% to about 40% by weight, the balance being oil. If, on the other hand, my binder is used alone, I prefer that the resin concentration thereof be not substantially in excess of about 33% by weight. For special purposes, however, such as in the preparation of tile-type linoleum, the resin concentration in my binder may be as high as about 40%.

The resin which I use in preparing my binder and designate herein as petroleum hydrocarboninsoluble resin derived from pine wood, may be prepared by extracting pine wood with a coal tar hydrocarbon such as, benzol or toluol, then evaporating the volatile constituents leaving a residue consisting of a mixture of wood rosin and the resin used in the present invention. Extraction of this mixture with a petroleum hydrocarbon such as, for example, gasoline, dissolves the rosin and after separation of the rosin, high in abietic acid, a resinous residue low in abietic acid remains. This resin is characterized by substantial insolubility in cold petroleum hydrocarbons,

but will differ somewhat in its specific characteristics, such as acid nurnber, melting point, exact petroleum ether solubility and content of naphtha and toluol soluble matter, depending upon the method for the recovery of resin from pine wood used in its production' This resin is more fully described and claimed in the copending application, Serial No. 61,745, filed on January 31, 1936, by Lucius C. Hall, now Patent No. 2,193,026.

Among the drying oils which may be used in the preparation of my improved binder are linseed oil, perilla oil, hempseed oil and others;

Among the semi-drying oils I may use either those of vegetable or marine origin, such as, forexample, soya bean oil, corn'oil, Menhaden oil, etc.

Both types of oils may be used in the raw state or they may first be bodied by heating.

The product obtained by heating the oil and resin together as described before, is a sticky, pitch-like product; To convert this to the gel product, suitable as a binderfor linoleum, ,I add an aldehyde with orwithout an alkaline catalyst to. the hot oleoresinous productafter it has reached the stage of polymerization beforev indicated. The alkaline catalyst may be used per so with the. aldehyde orit may be. combined in the same molecule with the aldehyde. Among. the aldehydes suitable in accordance withthis invention are para-formaldehyde, acetaldehyde, furfural, etc. The converting agent which I prefer to use, and with which I obtain the best results, is hexamethylenetetramine. In this unique compound the aldehyde and alkalinecatalyst are molecularly combined, and at the relatively high temperatures used in the present invention, some ammonia is liberated. It is to be understood, therefore, that'where I refer to an aldehyde with analkaline catalyst in the claims,. Imean that the. said catalyst maybe molecularly combined with the aldehyde or it may merely be in ad mixture with the aldehyde.

With thedrying oils conversion is obtained with-.the aldehydes alone-but in order to make the reaction product using. asemi-drying oil equivalent to. that produced witha drying oil, it is. necessary that an alkalinecatalyst, for ex-- ample, lime, sodium carbonate, zinc: oxide, etc. beusedin conjunction-with the aldehyde orthat the alkaline catalyst be combined in the samemolecule with the aldehyde, as in hexamethylene- The alkaline catalysts, combined or tetramine. uncombined, may ofcourse also be used'with the. drying oils, the same conversion occurring inlesgtime than with the aldehydes alone.

The. amount of converting agent used varies- With'the. converting agent. When using hexamethylenetetramine, I prefer about 1% to about 3%.. of the weight of the oleoresinous composi tion, and with an aldehydealone I prefer using about the same amount. With an aldehyde and added alkaline catalyst, I preferusing about 2% to about 3% of the aldehyde and about'2% to about 3% of the alkalinecatalyst.

Having described my invention in a'g-eneral manner, I will now proceedto a more detailed description thereof by reference to the following examples.

1 Ezrample I Thirty-three parts by weight of petroleum hydrocarbon-insoluble resin derived from pine .wood. and sixty-seven parts by, weight of a Menhaden. oil bodied; at aboutfifllii F.' to a..viscosity,.of..:S: Gardnen-Holdt, Scale) wei'ezheatediitogether gat Example II Thirty-three parts by weight of petroleum hydrocarbon-insoluble resin derived from pine wood and 67.0 parts by weight of bodied soya bean oil were heated together and converted as shown in Example I. The linoleum made with this binder is designated as linoleum B in Table 1.

Example III Thirty-three parts by weight of petroleum hydrocarbon-insoluble resin derived from pine wood, 6-0.3 parts by weight of bodied Menhaden oil and 6.7 parts by weight of raw castor oil were heated together and converted as shown in Example I. The linoleum made with this binder is designated as linoleum C in Table 1.

Example IV Thirty-three parts by weight of petroleum hy-- drocarbcn-insoluble resin derived from pine: wood, 33.5 parts by weight of bodied Menhaden oil and 335 parts by weight of bodied soya bean oil were heated together and then convertedas in Example I. The linoleum made with this binder is designated as linoleum D in Table 1.

Example V Thirty parts by weight of petroleum V hydrocarbon-insoluble resin derived from pine wood and 70.0 parts by weight of bodied Menhaden oilwere heated together and then converted as in Example I. The linoleum made with this binder is designated as linoleu-m E' in Table 1. r

A white inlaid linoleum of the following formulation was made using each of the plastics or binding agents above shown. The same formula was also made using a regular linoleum binding agent, this to-be used as a comparator for the series. Formula 1 is as follows:

Parts'by weight Binding agent Whiting.

Titanium oxide Ultramarine blue Each linoleum :was prepared inthe manner well. known in theart and then :sheeted to givea' thickness of- 0.12-0.16! gage. Each sheet was then. matured at F. .untilflit. passed the.

U. S. specifications. for' battleship. linoleum.-

hour. mustxnot be broken and. the indentation measured immediately after removal of the load mustv not exceed 0.006 inch, northe-indentation meas-v uredl hour thereafter exceed 0.001 inch;

was then subjected to an alkali resistance test and a softening test. The former was determined by putting an iron ring of 1 inch inside diameter on the surface of the linoleum with paraifin and then placing in the center a 5% aqueous solution of sodium hydroxide for minutes. The solution was removed at the end of this time, the sample blotted dry and the linoleum attacked, scraped away by rubbing gently with a knife. The portion of the linoleum unattacked by the alkali is practically untouched by this gentle scraping. The depth of attack is determined by taking the gage of the sample in the center of the spot and subtracting this from the average gage, of the original linoleum.

The softening test is determined by taking strips of the linoleum and obtaining the average indentation of these produced by a load of 2500 grams on a fiat circular plunger, 0.282 inch in diameter. These strips are then put on racks in an oven maintained at 180 F., and at 100% relative humidity, and kept there for one week. The strips are removed, blotted dry and 5 minutes thereafter again subjected to the indentation measurement. A similar measurement is also obtained at the end of 1 hour. The degree of softening is, of course, shown by the increase in the indentation.

The results of these tests on the various linoleums made according to Formula 1, containing the binding agents as made in accordance with this invention as well as an orthodox binder, are shown in Table 1.

*Showed bad blistering.

It will be noted that both in the alkali test and the softening test, the control sample in which an orthodox binder is used is definitely inferior to any of my binders. In the softening test it will be noted that the linoleum containing my binders suffered little or no softening, whereas the control not only showed considerable softening but bad blistering as well. The marked superiority of linoleum made with my binding agents is thus clearly indicated.

The following examples further illustrate binding agents made in accordance with my invention and which are suitable in linoleum fabrication.

Example VI A binding agent was made in the manner indicated in Example I using as the converting agent 4% of the oleoresinous composition of a mixture of equal parts by weight of lime and paraformaldehyde. A linoleum. prepared therewith, in the manner before indicated, showed good alkaline resistance and resistance to warm moist conditions,

Example VII A binding agent was made in the manner indicated in Example I using as the converting agent 4% of the oleoresinous composition of a mixture of equal parts by weight of lime and furfural. A linoleum prepared therewith, in the manner before indicated, was very resistant to alkalies and to failure under warm, moist conditions.

As further illustration of the superior products that may be made with my binding agents, additional modifications were made in my improved binders and these were then incorporated in a linoleum mix as shown below and an inlaid linoleum prepared in the same manner as indicated above. Binding agents were made-in accordance with the general procedure shown in Example I using (1) a heat bodied Menhaden oil, the procedure being as shown in Example 1; (2) a heat bodied Menhaden oil but air blowing during the cooking of the resin and oil as shown in Example I; (3) raw Menhaden oil, air blowing during the cooking of the resin and oil in accordance with the procedure in Example I. The binders so made are designated respectively as binders 10, 11 and 12 and the linoleum made therewith, according to Formula 2 below, are designated respectively as linoleums F, G and H.

A linoleum was also prepared in which the binding agent consisted of 25% of binder 10 and 75% of orthodox binder, designated as binder 13 and the linoleum made therewith, according to Formula 2, as linoleum I. Linoleum J was also prepared according to Formula 2 in which the binding agent, designated as binder 14, was composed of 25% of binder 11 and 75% of orthodox binder.

Formula 2 used for the preparation of linoleums F to J, inclusive, is as follows:

Parts by weight Binding agent 100 Wood flour Whiting"- Titanium oxide 1'7 Ultramarine blue 0.5

Table 2.

Table 2 Average indentation in 0.01 mm. i il'i i ep 0 Binder alkali pene- 5 minutes 1 hour tration in Oricinal alter realter remches moval from moval from test test Orthodox Control 0.0082 7. 0 23.5 16.0 10 F 0.0035 4. 5 6. 5 5. 5 0. 0035 0.0050 9.0 10.5 8. 5 0.0060 8. 0 15. 5 11. 5 0.0060 7. 0 14. 5 11. 5

The marked superiority of a linoleum containing my binders is again apparent. It will also be noted that the substitution of 25% of an orthodox binder with one of my binders, produces a pronounced improvement in the properties of the linoleum made'therewitli, indicating again the-remarkable alkaliresistance and resistance to warm, moist conditions obtained through ithe use of -my:- hinders. 7

It will-bewunderstoodzthatthe examples above shower are by; ayofiillustration only and that the-scope of iny-iinventionis not to be limited thereto. H r

What I claim desire to protect by Letters Patent-is: 7 u

,1; The rnethod-otmaking alinoleiun binding agent which comprises l heating a mixture of a hetroleu h drocarbon-insoluble resin derived wood oil selected from the class c .a and semi-drying oils at a t mperature betweenabout 525 and about-590 until the composition attains a heavy sticky tch-lilee consistency: and thereafter heating iccni pos itionrwith :a small proportion of an itassunios an elastic gel structure.

Themethod oi gent co: 7 p trcleurn hydroca fl'flm rpil lewood l ng-a mixture of a isoluble resin derived 1e "1 at atemperature -599 E: until the N sticky pitch-like isi stency; and thereafter eating composition wi smalluproporzion of an aldehyde and an inorganic alka elastic geistructure.

3; zneth'odf oil making a linoleum binding agentiwliich-comprises heatinga mixture of a petroleum hydrocarh'on-insoluble resin derived fioinnine wocdandia.sen1i drying at a temperatime between about 525"andabout 590 F; until the composition attains a heavystiokypitch-like consistency, and thereafter heatingsaid composi- 4I Thf3 method of making a linoleum binding agent whichco nprises heatinga mixture of a" petroleum hydrocarbon-insoluble resin derived m Di W nd Mfinh d Oilat a p r about 525? and about 590 F. until tion attains a heavy sticky pitch-like the corniabsi i L: n t until it assumes an consistency;- and thereafter heatingsaid compositiorrwith'a small'proportion of analdehyde and aninorganicalkalinecatalyst until it assumes an elastic-gel structure.

flie method of making a l linoleum binding agent whieh comprises-heating a mixture of a petroleum hydrocarbon-insoluble resin derived from pine Wood andanoil selected from the class consi-sting of drying and semi-drying oils at a temperature- 'b'etween about 525'"- and'about 590 F? until thecomposition attains a heavy sticky pitch-like consistency, and thereafter heating said composition with a sinall proportion of hexametliylenetetramine.

' BLT-lie method of makinga linoleum binding agent which comprises heating a mixture of a petroleum hydrocarbon-insoluble resin derived from" lne wood and lvienhaden oil ata temperature rbe-t'iiveen ab'out 'iizfii and" about 575 F. for frorniabout 4- to about Shows, and thereafter heati girhe r'esultantproductwith a small proportion oflhexamethylenetetramine until it assumes aii'e attic gel-Istructure:

7..Tiie rmlethod of making a linoleum binding a ent Iwhichcomprisesi heating a mixture of a clown hydrocarhcneinsoiuble resin derived fr'ormpine Woodiand linseedoil at a temperature hetweeniabtiutfiZEP and' about 575" for from about a to about 5 hours, and thereafter heating thetiTesultant' product with a small proportion of liexamethylenetetramine until it assumes an elastic-:gel structure.

81 Afbindingagentifor linoleum pr pared by the method defined by claim 1..

9. A bindingagent for, linoleum the method defined by claim 2.

10. A binding agent for linoleum the method defined by claim 3.

11.- A binding-agent for linoleum the method defined by claim 4.

12. A binding agent for linoleum the method defined by claim 5.

13. A binding agent for linoleum the method defined by claim .6.

14. A binding agent for linoleum the method defined by claim '7.

ABRAHAM B. MILLER.

prepared by prepared by prepared by prepared by prepared by prepared by 

